2-halogenoethoxy silicon compounds



Patented Aug. 7, 1945 orric Z-HALOGENOE'JTHO SFLKCQN QOIEDWNlD Winton I.Patnode and Robert Sauer, achenectady, N. K, assignors to GeneralElectric Company, a corporation oi New Yorh No Drawing. Application Mayit, 1M2, Serial No. 443,023

5 Claims.

This invention relates to 2-halogenoethoxy silicon compounds. It isparticularly concerned with novel Z-halogenoethoxy silanes (includingsubstituted silanes) having the general formula RaR'bS-i (OCHzCHaX)(i-c-bi wherein R is a member of the class consisting of hydrogen andmonovalent hydrocarbon radicals, R is a member oi the class consistingof monovalent hydrocarbon radicals and XCH2CH2O- radicals, X is ahalogen atom selected from the group consisting of chlorine and bromine,and a. and b are integers equal to at least one and not more than threeand the sum of a+b is not greater than 3.

The monovalent hydrocarbon radicals represented by R and R in the aboveformula may be any suitable alkyl and aryl (including alkaryl andaralkyl) radicals, e. g. methyl, ethyl, propyl, butyl, phenyl, tolyl,xylyl, mono-, di-, and triethyl phenyl, naphthyl, etc. radicals.

Our copending application Serial No. 443,022, filed concurrentlyherewith, describes and claims a method for the preparation ofZ-chloroethyl silicate, having the formula (ClCH2CH2O)4Si, by reactingsilicon tetrachloride with ethylene oxide. The present applicationrelates to novel 2-halogenoethyl ethers obtained from substitutedhalogenosilanes and thylene oxide. The reaction between thehalogenosilane and ethylene oxide suitably may be represented by theequation:

wherein R, R, X, a and b represent the radicals and integershereinbefore indicated.

Since even the freshly distilled halogenosilanes contain a smallconcentration of hydrogen halide, probably resulting from hydrolysis ofthe halogenosilane by moisture taken for example from the atmosphere, itis possible that the hydrogen halide acts as a catalyst for th reactionbetween the silane and ethylene oxide. However, the fact that thereaction proceeds smoothly and quickly to give good yields of the2-halogenoethyl esters without the introduction of additional hydrogenhalide would seem to indicate either that the small amount of hydrogenhalide unavoidably present is suflicient for catalytic purposes or thatno catalyst is necessary for the reaction.

In order that those skilled in the art better may understand how ourinvention'may be carried into efiect, the following specific examplesare tive Z-haIogenoethoxy silicon compounds coming within the class ofcompounds represented by the formula RaR'bSKOCHiCHaX) l4-ab).

Exampl 1.--M'ethyl tri-2=chloroethorysilanc.

Into a glass reaction vessel equipped with a reflux condenser and a gasinlet tube were placed 183 g. of methyltrlchlorosilane. Ethylene oxidegas was introduced through the inlet tube and bubbled through the liquidat till-100 C. for 12 hours. Fractional distillation of the product atreduced pressure save an 87 per cent yield of methyl tri-Z-chloroethoxysilane having a boiling point of 136-137" C. at 6 mm.pressure.

Example 2.Trimethyl-Z-chloroeihorysilaaa- The procedure of Example 1 wasrepeated using 44.3 g. of trimethyl chlorosilane. The ethylene oxide gas(excess) was bubbled through at a temperature of 55-60 C. for 5 hours.The product which was isolated in 80 per cent yield boiled at atemperature of 131-132 C. at 748 mm. pressure.

Example 3.Methyldi 2 chloroethozrysilane andtri-Z-chloroethowysilana-Into a pressure bottle, the stopper of whichwas connected by means of a piece of rubber tubing to a tank of ethyleneoxide, were placed 200 g. of a mixture of methyldichlorosilane,trichlorosilane and silicon tetrachloride. This mixture was shaken underthe full pressure of the liquid ethylene oxide in the tank (14-15lbs/sq. in.). At first the reaction was quite vigorous and the reactionflask had to be cooled, or the reaction slowed down temporarily bydecreasing'the gas pressure. At the end of 35 hours the reaction wascomplete. By fractionation of the reaction products at reduced pressure,the following compounds were obtained:

E'a:a,mple 4.-Trimethyl-Z-chloroethoxysilane and tetmkis-Z-chloroethylsilicate.-Into the apparatus of Example 1 were placed 225 g. of amixgiven illustrating the preparation of representature of silicontetrachloride and trimethyl chlorosilane containing 65.6 per centchlorine. Excess ethylene oxide was bubbled through this mixture for 10hourskeeping the temperature at -90. By distillation at atmosphericpressure, 89.7 g. of trimethyl-Z-chloroethoxysilane (B. P. 130.5-133/,775 mm.) were obtained. By distillation at reduced pressure theresidue yielded 251.2 g. of

tetrakis-z-chloroethyl silicate (B. P. 175-17775 mmJ. I

It is to be understood that our invention is not limited to theformation of the specific coming of monovalent alkyl and aryl radicalsand XCHsCI-L-O- radicals, X is a halogen atom selected from the classconsisting of chlorine and bromine, a and b are integers and are equalto pounds described in the above examples. Ex- 5 at least 1, and the sumof a+b is not greater ampleg of other compounds, together with theirthan 3.

formulae and boiling points which have been pre- 2.Phenyltri-2-chloroethoxysilane.

pared by reacting ethylene oxide with appro- 3.Trimethyl-2-chloroethoxysilane.

priate halogenosilanes, or alkyl or aryl sub- 4.Methyldi-2-chloroethoxysilane.

stituted halogenosilanes are the following: 10 5. The method ofpreparing halogenoethoxy Compound Formula Boiling pointDimethyl-Z-chloroethoxysilane (onmsuoomcnicmn 212-213 (L/758 mm.

Methyldi2 chloroethoxysilane Phenyltti-Z-chloroethoxysilaneMethyitri-2-bromoethoxysilane. Dimethyldi-Z-bromoethoxysilaneDiphenyldi-2-chloroethoxysilana The novel ethers described herein areuseful 10 silicon compounds which comprises eflecting reas solvents,high-boiling liquids, and lubricants. They are readily hydrolyzed andmay be used as intermediates in the formation of more complex orresinous organosilicon compounds similar to those describedfor examplein Patent 2,258,218 issued to Eugene G. Rochow.

.What we claim as new and desire to secure by Letters Patent of theUnited States, is:

1. Halogenoethoxy silicon compounds corresponding to the general formulaRm'tsuocmcmx) (4-rr-b) wherein R is a member of the class consisting ofhydrogen and monovalent allgvl and aryl radicals, R is a member of theclass consist- 85 action at an elevated temperature between ethyleneoxide and a halogenosilane having the general formula wherein R.represents a member of the class consisting of hydrogen and monovalentalkyl and aryl radicals, R represents a member of the class consistingof monovalent alkyl and aryl radicals, X represents a halogen atomselected from the class consisting of chlorine and bromine, and a and bare integers and are equal to at least 1, the sum of 11+!) being notgreater than 3.

WINTON I. PATNODE. ROBERT O. SAUER.

